Additions to Alkenes "Master Organic Chemistry" Note - this sheet is not meant to be comprehensive.

Your course
masterorganicchemistry.com may provide additional material, or may not cover some of the
Reaction "Regiochemistry" "Stereochemistry" reactions shown here. Your course instructor is the final authority.
H OH
R R 1) BH 3 R R Sometimes you might see BH 3•THF or B 2H 6 used here: it's the same reagent in a slightly different form.
Anti-Markovnikoff syn addition
Hydroboration The base (can be NaOH, KOH, identity unimportant) helps make H 2O2 more reactive. The reaction is anti -
R H 2) NaOH, R H
Markovnikoff because the H–B bond is polarized toward H (electronegativity of H = 2.2, B = 2.0) - the H
H 2O 2 adds to the carbon best able to stabilize positive charge (i.e. the most substituted one).
1) Hg(OAc) 2
H 2O HO H
R R This reaction goes through 3-membered "mercurinium" ion. The NaBH 4 step removes the
Oxymercuration Markovnikoff syn + anti mercury. While the addition is anti, the overall reaction is stereorandom because this step involves a carbon
R H 2) NaBH 4 R R
R H based free radical (usually not discussed). Alternatively, an alcohol used in place of water will produce an ether.

HO H
R R H 2SO4 Strong acid protonates the alkene, generating free carbocation. Watch out for
Markovnikoff syn + anti
Acid-catalyzed addition of H 2O R possibility of rearrangements when a tertiary carbocation could be generated through a 1,2 shift.
R H H 2O R
(hydration) R H HSO 4– anion is not strongly nucleophilic, hence it does not add. Gives a mixture of syn and anti products
due to the free carbocation.
Cl H
R R HCl Markovnikoff syn + anti
Addition of HX
R H R R
R H HCl and HBr (as well as HI, not pictured) protonate the alkene to give a free
carbocation which can then be trapped by the halide anion. Gives a mixture of syn and anti
Br H
R R HBr
Addition of HX Markovnikoff syn + anti
R H R R
R H
Br
Br R R Bromonium ion mechanism
Br 2 R R R H
Bromination N/A anti addition
R H Br or H 2O/ROH depending on solvent
R R Br
The key detail in these reactions is solvent: water and alcohol solvents will form the
R H HO halohydrin products (the ones containing the OH and Br). All other solvents (you might
Br 2 R
Halohydrin Formation R
Markovnikoff anti addition see CCl4, CHCl 3, hexane, etc. ) provide the dibromide.
H 2O R H
Br
Cl
R R Cl2 R R As with bromination, above. Although not depicted, use of water or alcohol as solvent
Chlorination N/A anti addition
R H R H will also lead to formation of the halohydrin product (also anti).
Cl

HO OH
R R OsO 4 R R Osmium is a transition metal. The tools won't be given in this course to fully understand how this reaction
Dihydroxylation N/A syn addition
R H works. Occasionally a second reagent like NaHSO 3, H 2S, or Na 2S2O3 is also given as a reactant in this
R H reaction - minor detail, it's used to remove the osmium from the hydroxyl groups.

HO OH Keywords are "cold, dilute". NOTE: If "heat" or "acid" is mentioned in the conditions, the diol will
R R KMnO 4 R R N/A syn addition be cleaved to provide carbonyl compounds (same reaction as ozonolysis with oxidative workup,
Dihydroxylation R H cold, dilute R H below).
NOTE: "anti" hydroxylation can be achieved through epoxidation followed by treatment with NaOH (basic)
or aqueous acid ( H 3O+ )
O
OH O
R O O R RCO 3H is a peroxyacid. A common peroxy acid for this reaction is m-CPBA
R R R N/A syn addition Cl OH
Epoxidation (m-chloroperoxybenzoic acid). If H 3O+, heat is written afterwards, this
R H R H O
is opening of the epoxide to give the diol (anti-selective) m-CPBA

H2 H H
R R R R N/A syn addition The catalyst can vary - you might see Pt or Ni as well. All provide the same product with the same
Hydrogenation
R H Pd/C R H stereochemistry.

H Br
R H HBr Peroxides generate the Br• radical, which adds to the double bond in the way that will generate the
Radical addition of HBr Anti-Markovnikoff syn + anti most stable radical (i.e. the radical will go on to the most substituted carbon). This explains the
H H peroxides R H
H H selectivity for the anti-Markovnikoff product. It gives a mixture of syn and anti because it goes through
(RO-OR) a free radical process.
O3
Ozonolysis (Reductive workup) R R
O + O
S R H Reductive workup: Zinc (Zn), or dimethyl sulfide (DMS, Me 2S) is a reducing agent. It reduces excess ozone, allowing for isolation
R R CH3 CH3 (or Zn/H+)
of the aldehyde.
R H
O3 R R Oxidative workup: Hydrogen peroxide is used to obtain the carboxylic acid instead of the aldehyde.
O + O Can also use KMnO 4 and acid
Ozonolysis (Oxidative Workup) R OH
H 2O 2 Omissions, Mistakes, Suggestions?
This reaction goes through addition of a carbene (actually, "carbenoid") to james@masterorganicchemistry.com
H H
CH2I 2 C the double bond. The reaction is stereospecific.
R R R R This sheet copyright 2019, James A. Ashenhurst
Cyclopropanation N/A syn addition Another set of conditions to provide a cyclopropane is CHCl3 with strong
R H masterorganicchemistry.com
Zn/Cu R H base (NaOH), which makes the dichlorocyclopropane.